Control of animal pests with 3H-oxazol-{8 4,5-6{9 pyridine-2-one esters of 3-(-o-)or (-s-)-0,0{40 di(lower alkyl) phosphates and thiophosphates

ABSTRACT

WHEREIN R1 represents halogen or nitro, R2 represents hydrogen or lower alkyl, R3 represents alkyl, alkoxy, alkenyloxy, alkynyloxy, phenyl, amino, monoalkylamino or dialkyl-amino, R4 represents alkyl, alkenyl or alkynyl, and X and Y each represent oxygen or sulphur. D R A W I N G Methods and compositions utilizing sulphur containing phosphorus compounds of pyrido-oxazole derivatives for combating various animal and vegetable pests, with particular emphasis against insects and representatives of the order Acarina, are disclosed. The new compounds correspond to the formula

United States Patent [1 1 Kristinsson et al.

[ May 27, 1975 CONTROL OF ANIMAL PESTS WITH 3H-OXAZOL-[4,5-6]PYRlDlNF-2-ONE ESTERS OF 3-(-0-)OR (-S-)-0,0DI(LOWER ALKYL) PHOSPHATES AND THIOPHOSPHATES [75} Inventors: Haukur Kristinsson, Bottmingen;

Kurt Rufenacht, Basel, both of Switzerland {73] Assignee: Ciba-Geigy Corporation, Ardsley,

(22} Filed: Jan. 2], I974 [2]] Appl. No.1 435,065

Related U.S. Application Data [60] Division of Ser. No. 156,983,,lune 25, i971, Pat. No.

3.808218, which is a continuation-impart of Ser No. 155,604, June 22, I971, abandoned.

2,984,669 5/l96l Brahler et al. 260/307 C Primary Examiner-Stanley J A Friedman Assistant Examiner-Allen J. Robinson Attorney, Agent, or FirmHarry Falber; Frederick H. Rabin [57] ABSTRACT Methods and compositions utiliz"' sulphur containing phosphorus compounds of pyrido-oxazole derivatives for combating various animal and vegetable pests, with particular emphasis against insects and representatives of the order Acarina, are disclosed. The new compounds correspond to the formula wherein R, represents halogen or nitro, R represents hydrogen or lower alkyl, R represents alkyl, alkoxy, alkenyloxy, alkynyloxy, phenyl, amino, monoalkylamino or dialkyl-amino, R represents alkyl, alkenyl or alkynyl, and X and Y each represent oxygen or sulphur.

16 Claims, No Drawings CONTROL OF ANIMAL PESTS WITH 3H-OXAZOI.-[4,5-6]PYRII)INE-2-ONE ESTERS OF 3-(0-l0R (-S-)-0,0'I)I(LOWER ALKYL) PHUSPHATES AND THIUPHOSPI-IATES This is a division of application Ser. No. 156,983, filed on June 25, 1971 now US. Pat. No, 3,808,2l8 which in turn is a continuation-in-part of application Ser. No. l55,604, filed on June 22, i971, now aban- Cloned DESCRIPTION OF THE INVENTION The present invention relates to new organic phosphorus compounds, processes for their manufacture, insecticidal and acaricidal preparations that contain these new compounds and their use in combating animal and vegetable pests.

The new organic phosphorus compounds correspond to the formula wherein R, represents hydrogen, halogen or nitro, R represents hydrogen, methyl, chloromethy] or bromomethyl, R represents alkyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkoxy, halogenalkoxy, phenyl, amino, monoalkylamino or dialkylamino, R represents alkyl, alkenyl, alkynyl, alkoxyalkyl or halogenoalkyl and X and Y each represents oxygen or sulphur.

For R, representing halogen, fluorine, chloride, bromine or iodine, but especially chlorine or bromine, are suitable.

Alkyl, alkenyl or alkynyl chains that are possible for R and R, contain as lower hydrocarbon radicals or as the hydrocarbon part of alkoxy, alkenyloxy, alkynyloxy, alkoxyalkoxy and alkylamino radicals R and R at the most 6, preferably at the most 4, carbon atoms and may be straight or branched.

Exemplary of such radicals are, interalia, methyl, ethyl, n-propyl, isopropyl, n-, r'-, sec.-, tert,-butyl, allyl, crotonyl, methallyl, propargyl. n-butynyl.

Particular importance attaches to compounds of the formula I wherein R, represents hydrogen, chlorine, bromine or nitro, R has the meaning given under formula 1 above, R represents an alkyl, alkoxy, alkenyloxy, alkoxyalkoxy, or halogenoalkoxy radical, each radical R containing at the most 4 carbon atoms, or a phenyl radical, amino radical or dialkylamino radical with 2 to 4 carbon atoms, R represents an alkyl, alkenyl, alkoxyalkyl or halogenoalkyl radical with at the most 4 carbon atoms and X and Y represent oxygen or sulphur.

The compounds of the formula I are manufactured by reacting an oxazolo (4.5-b)pyridine derivative of the (III) wherein A represents the halogenmethyl radical, the vinyl group or a l,2-dihalogenethyl radical, with a phosphorus compound of the formula HS P ii oR (IV) y 4 optionally in the presence of an acid binding agent, or with a salt thereof. In the formulae Ill and IV, the sym bols R to R,,, X and Y, having the meanings given for formula I.

The phosphorus compounds of the formula IV react with the oxazolo4,5-b)pyridine derivatives of the formula Ill without further difficulties at temperatures between 0 and 120C, preferably at l0 to C. It is advisable to carry out the process according to the invention in the presence of a solvent or diluent that is inert towards the reactants. Possible solvents or diluents are primarily aliphatic ketones, such as acetone, methyl ethyl ketone; alkanols such as methanol, ethanol, isopropanol; esters, such as ethyl acetate; nitriles; N- alkylated acid amides; aromatic hydrocarbons, such as benzene, toluene and water, and mixtures of such solvents with water.

The reaction of a compound of the formula III, in which A represents halogen-methyl or 1,2-dihalogenmethyl, with a compound of the formula IV takes place accompanied by the exchange of the, or a, halogen atom; in the process, the halogen atom in the l-position in the 1,2-dihalogen-ethyl radical is exchanged. The reaction is therefore carried out by adding acid binding agents or with salts, especially with alkali metal salts and ammonium salts of the phosphorus compounds of the formula III. Preferred acid binding agents are the alkali metal hydroxides and carbonates; however, tertiary nitrogen bases can also be used. If A represents the vinyl group, the phosphorus compound of the formula IV adds on to the vinyl double bond.

As examples of possible starting materials of the formula III, the following may, inter alia, be considered for the process according to the invention:

3-chloromethyl-oxazolol 4,5-b1pyridin-2t3H )-one 3-chloromethyl-oxazolo[ 4,5-b]pyridin-2( 3H l-thione 3-chloromethyl-6-chloro-oxazolo[4,5-b]pyridin- 2t 3H)-one 3-bromomethyI-6-chloro-oxazolo[4,5-blpyridin- 2(3H)-one 3-chloromethyl-o-bromo-oxazolo[4,5-blpyridin- 2(3Hl-one 3-chloromethyl--nitro-oxazolo[4,5-bIpyridin- 2(3H)-one 3-vinyl oxazolo[4,5-b ]pyridin-2( 3H )-one 3-vinyl-oxazolo[4,5-b]pyridin-2( 3H )-thione 3-vinyl-6-chloro-oxazolo[4,5-b]pyridin2( 3H )-one 3-vinyl-6bromo-oxazolo[ 4,5-b ]pyridin-2( 3H )-one 3-vinyl-6-nitro-oxazolol4,5-b1pyridin-2t 3H )-one 3-( l ,2'-dichloroethyl )-oxazolo[4,5-b lpyridin-Z- 3-( l ',2'-dibromoethyl )-oxazolo[4,5-b]pyridin- 3-( l '.2'-dichloroethyl )-oxazolo[ 4,5-b lpyridin- 2( 3H l-thione 3-( l ',2'-dibromomethyl)-oxazolo[ 4,5-b ]pyridin- 2( 3H )-thione 3-( l ,2'-dichloroethyl)-6-chloro-oxazolo[4,5-

blpyridin-2t3Hl-one 3-( l ,2"dibromoethyl)-6-chloro-oxazolo[4,5-

3-( l ',2-dichloroethyl )-6-bromo-oxazolo[4,5

blpyridin-ZlliHl-one 3-( l ,2'-dibromoethyl )-6-bromo-oxazolo[4,5-

blpyridin-2(3H)-one 3( l ',2'-dichloroethyl )-6nitro-oxazolo[4,5-

3-( l ',2'-dibromoethyl)-6-nitro-oxazolo[4,5-

The following thio Tiosphoric acids, thiophosphonic acids and thiophosphoric amides may be mentioned, inter alia, as examples of phosphorus compounds of the formula IV:

0,0-dimethyl-dithiophosphoric acid 0,0-dimethyl-monothiophosphoric acid 0,0-diethyl-dithiophosphoric acid 0,0-diethyl-monothiophosphoric acid 0,0-di-isopropyldithiophosphoric acid O-methyl-O-ethyl-dithiophosphoric acid O-methyl-O-isopropyl-dithiophosphoric acid O-methyLO-isopropyl-dithiophosphoric acid 0,0-diallyl-dithiophosphoric acid 0,0-bis-(2-methoxy-ethyl)-dithiophosphoric acid 0,0bis-( 2-ethoxy-ethyl)-dithiophosphoric acid 0,0-bis-( Z-chloroethyl)-dithiophosphoric acid O-methyl-dithio-methylphosphonic acid O'ethyl-dithio-methylphosphonic acid O-methyl-dithio-ethylphosphonic acid O-ethyl-dithio-ethylphosphonic acid O-methyl-dithio-phenylphosphonic acid O-ethyLdithiO-phenylphosphonic acid O-methyl-thiophosphoric acid amide O-ethyl-thiophosphoric acid amide O-isopropyl-thiophosphoric acid amide O-methyl-thiophosphoric acid-methyl amide O-ethyl-thiophosphoric acid-methyl amide O-methylthiophosphoric acid-ethyl amide O-ethyl-thiophosphoric acid-ethyl amide O-methyl-thiophosphoric acid dimethyl amide O-ethyl-thiophosphoric acid-dimethyl amide O-methyl-thiophosphoric acid-diethyl amide O-methyl-thiophosphoric acid-diethyl amide O-methyl-dithiophosphoric acid-dimethyl amide O-ethyl-dithiophosphoric aeid-dimethyl amide O-methyl-dithiophosphoric acid-diethyl amide O'ethyl-dithiophosphoric acid-diethyl amide O-isopropyl-dithiophosphoric acid-dimethyl amide The phosphorus compounds of the formula IV can be manufactured according to known processes.

The starting materials of the formula III have not been described hitherto. The oXazolo[4,5-b]-pyridine derivatives of the formula III, in which A represents a halogen-methyl radical, are manufactured by converting an oxazolo[4,5-blpyridine of the formula V rivatives. As halogenating agents there may be used:

thionyl chloride, phosphorus trichloride and phosphorus tribromide, phosphorus pentachloride and phosphorus pentabromide, phosphorus oxyhalides, etc. Since in the case of these oxazolo[4,5-b]pyridines there occurs no salt formation with the hydrogen halide that is split off, the addition of an acid binding agent can be dispensed with.

The starting materials of the formula III, in which A represents the vinyl group or a l,2-dihalogen-ethyl rad ical, are obtained by reacting an oxazolo[4,5- b]pyridine of the formula IV with vinyl acetate in the presence of mercury salts of strong acids [l-l. Hopff et al., Helv.chim.Acta 18, l35-l40 H960} to give the corresponding 3-vinyl-oxazolo[4,5 b]pyridine derivatives. It is also possible, moreover, to obtain such compounds by splitting off 3-(2'-hydroxyethyl) and 3-(2'- acetoxyethyl) derivatives) by heating or by reacting an oxazolo[4,5-b]pyridine of the formula V with acetylene. The 3-( l ,2-dihalogenethyl)-oxazolo[ 4,5- blpyridine derivatives are then obtained by the addition of halogen, such as chlorine or bromine, to the vinyl group.

These reactions are carried out preferably in a so|- vent or diluent that is inert, or in solvent mixtures that are inert, towards the reactants. The hydroxymethyl group is introduced advantageously in an aqueous me dium; the subsequent halogenation to the halogenmethyl group, likewise the addition of halogen to the vinyl group, in a halogenated hydrocarbon, such as chloroform, carbon tetrachloride, halogenated ethylenes and the like. In addition, aromatic hydrocarbons such as benzene, chlorobenzene and the like can also be used.

The reaction temperatures are in the range from 0 to 120C. The starting materials of the formula III are obtained in good yield and purity. They can be used directly for the reactions according to the invention without further purification.

The oxazolo[4,5-b]pyridine-2( 3H )-ones represented by formula IV can be theoretically in a tautomeric form, represented by the formula lVa, as oxazolo[4,5- b]pyridine-2(4H)-ones. In this case, the acid NH-group would therefore be in the pyridine ring instead of in the oxazolo ring. The claimed compounds of the formula I could accordingly also be written as 4-substituted isomers, corresponding to an alternative formula la. However, since all claimed compounds and all their primary products always occur only in a single form, they are cited here for reasons of consistency and simplicity as 3-substituted isomers, both by formula and nomenclature.

' :rz, \l Ii) 55 t W 1 0 R c x 1 Js/ (1a) N R l i The compounds of the formula l are suitable for combating various animal and vegetable pests. They are particularly suitable for combating insects and representatives of the order Acarina. These acive substances have a good to very good contact action and ingested action combined with systematic action, and are of particular importance in combating insects that eat plants and suck the juice of plants, representatives of the order Acarina, as well as the development stages of these pests. By such pests are to be understood in particular those that belong to the following families:

Acrididac: eg. Locusta spp.

Schistoccrea spp. Phlocothripidae: c.g. Hcliothrips haem. Miridae: c.g. Distantiella theobroma Sahlbergclla singularis Piesmidae: c.g. Piesma quadrata Lygacidac: e.g. Lygus spp. Pyrrhocoridae: e.g. Dysdercus spp. .lassidac: e.g. Cicadula spp.

Typhlocyba spp. Empoasea spp. Psyllidae: cg. Psylla spp. Aleyodidac: cg. Trialeurodes sppv Aphididac: cg. Macrosiphon spp.

Aphis spp. Myzodes spp. Eriosomatidae: eg. Eriosoma spp. Pscudoococcidac: eg. Planococcus citri Lecaniidae: c.g. Coccus spp. Stictococcidae: cg. Stictococcus spp. Diaspididae: e.g. Quadrispidiotus pern. Tenthrcdinidae: e.g. Athalia rosac Hoplocampa spp. Silphidae: cg. Blitophaga opaca Chrysomelidae: cg. Leptinotarsus dcc.

Melasoma spp. Lema spp. Phyllotreta spp. Diabrotica spp. Curcuionidae: cg. Sitona lincata phyllobius spp. Otiorrhynchus spp. Ccutorrhynchus spp. Anthonomus spp, Phytonomus spp. Cylas spp. Apiun spp. Scolytidac: eg Scolytus spp.

Dendroctonus spp. Blastophagus spp. Hypothemus hampci Scarabacidae: e.g, Mclolontha spp.

Rhizutrogus spp. Pachnoda spp. Pyralidae: cg. Diatraea saccharalis Pyraustidae: cg. Ostrinia nubilalis Crambidae: cg. Chilo spp. Schoenobiidac: cg. Schocnobrus spp. Tortricidae: cg. Pandcmis spp.

Carbocapsa porn. Grapholita spp. Epinotia spp. Conchylis ambiguella Zeiraphcra diniana Tortrix spp. Gelechiidac: cg. Phthorimaca spp.

Pcctinophora goss. Gracilariidac: c.g. Lithocollctis spp. Lyonctiidac: eg. Lyonetia spp.

Leucoptcra cuff. Yponorncutidac. cg. Hyponomcuta sppi Argyrcsthiidac: cg. Argyresthia cphlp. Plutellidac: e.g, Plutella maculipcnms Acmlepiidac: cg Acrnlcpia assectclla Hepialidac: c.g. Hcpialus spp. Lasiucampidac: I Pieridac: cg Picns spp.

Catopsilia spp. Gcomclridae: cg Opcriphthcra spp.

Eranms spp. Sclcnia spp. Lymantriidac: cg [.ymantria dispar Nnctuidac: cg Spoduptcra littoralis Hcliothis zca Mamcstra spp. Scotiu spp. Orthosia spp.

-Contmued Trypctidac: cg. Ccratitis capitata Dacus olcac Drosophilidac: cg. Drosophila spp. Agromyzidac: cg. Phytomyza rufipcs Agromyza mcgalopsis Saptomyza fiuvcola Chloropidae: cg. Oscinis frit C hlorops spp. Muscidac: cg Hylemya brassicac Hylemya anti ua Hylemya flora is Pegornya hyoscyani Tarsonemidae: e.g. Tarsonemus fragaria Tetranychidae: e.g. Tctranychus urticae Panonychus ulmi Eriophyidac: c.g. Eriophycs ribis Accria sheldoni Phyllocoptrupa oleivorus Furthermore, the new active substances can also be used for combating various storage pests such, for example, as gram weevils, bean weevils and bacon bee tles, as well as insects of the family Blattidae.

Due to their slight toxicity to warm blooded animals, the new organic phosphorus compounds of the formula I are of particular importance in combating insects occuring ectoparasitically on animals, representatives of the order Acarina and their development stages. By such pests are to be understood in particular those that belong to the following families:

Muscidae: cg Musca domestica Stomoxys calcitrans Calliphoridae: eg, Calliphora erythrocephala Lucilia cuprina callitroga hominivorax Gastrophilidae: cg. Gastrophilus intestinalis Hypodermatidae: e. g. Hypoderma bovis Dermatobia irritans Hippoboscidae: eg. Melophagus ovinus Oestridae: cg. Oestris ovis Tabanidae: eg. Tabanus bovinus Culicidae: cg. Anopheles spp,

Culcx spp. Aedes spp. Simuliidae: cigv Simulium sericatum Lipcuridae: eg. Lipeurus baculus (Mallophag) Phthiriidae: cg Phthirus pubis Pediculidae: e.g. Pediculus corporis Pulicidae: cg. Ctenocephalides can is Ctenocephalides fclis Tungidae: e.g. Tunga penetrans Argasidae: e.gv Ornithodorus moubata Argas reflexus lxodidae: e.g. lxodes ricinus (Bi-phase) Dermacentor reticulatus (B-phase) Rhipicephalus spec. (2-phase) Rhipicephalus appendiculatus Rhipicephalus everhi Boophilus microplus l-phasc) Boophilus decoloratus Amblyoma spec. Dermanyssidae: eg. Dennanyssus gallinae Bdellonyssus bacoti Dcmodicidae: eg. Demodex canis Trombiculidac: cg. Trombicula autumnalis Sarcoptidac: e. g. Sarcoptcs spp. Psoroptidac: eg. Psoroptcs spp.

in admixture with other insecticides or acaricides.

the activity spectrum of the active substances according to the invention can be broadened and. in particular. the insecticidal and acaricidal action improved. Exemplary of suitable additives for broadening the action are. for example: insecticidal and/or acaricidal esters and amides of phosphoric acid, phosphonic acid, thioand dithiophosphonic acid halogenated hydrocarbons and and analogues of DDT active substance, as well as pyethrines, esters of halobenzilic acid. oxicarbamates.

arylcarbamates and and carbamates of enolisable heterocycles.

Some of the new phosphorus compounds of the formula l are further suitable for combating endoparasites, especially parasitic helminths and their development stages such, for example, as representatives of the families Ascaridae, Trichostrongylidae, Aneylostanatidae, in domestic and farm animals such as cattle, sheep, goats, horses, pigs, cats, dogs and poultry.

The active substances are non-toxic in the concentra tions used for combating endoparasites, and are very well tolerated by domestic and farm animals.

The active substances of the formula I can be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid and correspond to the substances conventionally used in formulation technique.

The preparations according to the invention are manufactured in known manner by intimately mixing and grinding the active substances of the formula I together with suitable carriers, optionally with the addition of dispersing agents or solvents that are inert towards the active substances. The active substances can be in the form of and used in the following preparations: solid preparations:

dusting agents, scattering agents, granulates, coated granulates, impregnated granulated granulates and homogeneous granulates; liquid preparations:

a. active substance concentrates that are dispersable in water: wettable powders, pastes, emulsions;

b. solutions.

To produce dusts, scattering agents and granulates the active substances are mixed with solid carriers. Examples of carriers which can be employed are kaolin, talcum, bole, loess, chalk, limestone, ground limestone, Attaclay, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulfates, magnesium oxide, ground synthetic plastics, fertilizers such as ammonium phosphates, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal, etc. Those carriers can be used alone or admixed with each other.

The particle size of the carriers is, for dusts advanta' geously up to about 0.1 mm, for scattering agents from about 0.075 to 0.2 mm, and for granulates 0.2 mm or coarser.

The concentrations of active substance in the solid preparations are usually from 0.5 to 80%.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having to l5 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radi cal, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (Carbowaxes) fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidoncs, polyvinyl alcohols, condensation products os urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsiflable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, optionally, solvents. The concentration of active substance in these agents is 5 to wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphtha lene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are so mixed, ground, sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 is not exceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those given in the previous paragraphs, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between l20 and 350C. The solvents must be practically odorless, not phytotoxic, inert to the active substances and not readily inflammable.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of general Formula I are dissolved in suitable organic solvents, mixtures of solvents or in water, Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, alone or mixed with each other, can be used as organic solvents. The solution should contain the active substances in a concentration of from I to 20%.

The preparation according to the invention may also be mixed, for example, with fungicides, bactericides, fungistatics, bacteriostatics or nematocides, in addition to the insecticides and acaricides, in order to broaden the activity spectrum. The preparations according to the invention may also contain plant fertilisers, trace elements etc.

The content of active substance in the above described preparations varies from 0.] to and in this connection it should be mentioned that an application from an aircraft or by some other suitable means of application, concentrations of up to 99.5% or even pure active substance may be used.

In the Examples that follow, preparations of the new active substances of the formula I are described. The parts denote parts by weight.

Dusting agents The following substanes are used for the manufacture of (a) a (b) a 2% dusting agent:

a. 5 parts of active substance of the formula I, e.g. O,- O-dimethyl-S-(6-chloro-oxazolo [4,5-b]-pyridin- 2(3H)-onyl-(3)-methyl)-dithiophosphate parts of magnesium carbonate 85 parts of talcum b. 2 parts of 0,0-diethyl-S-(6-chloro-oxazolo[4,5- b]pyridin-2(3H)-onyl-(3-)methyl)-dithiophosphate 1 part of highly dispersed silica 97 parts of talcum The active substances are mixed with the carriers.

Granulate The following substances are used to manufacture a 5% granulate:

5 parts of the active substance of the formula I, e.g.

0,0-diethyl-S-(6-chloro-oxazolo[4,5-b]pyridin- 2(3H)-onyl(3-)methyl)-dithiophosphate 0.5 parts of epoxidised vegetable oil 1 part of highly dispersed silica 93.5 parts of kaolin (0.4 0.8 mm particle size) The active substance is mixed with the vegetable oil and the silica and dissolved in 6 parts of acetone. The resulting suspension is sprayed onto kaolin and the acetone subsequently evaporated in vacuo.

Wettable Powder The following constituents are used to manufacture a (a) 40%, (b) a 50%, (c) a 25% and (d) a 10% wettable powder:

a. 40 parts of active substance of the formula I, e.g.

0,0-dimethyl-S-(oxazolo[ 4.5-b ]pyridin-2( 3H )-onyl- (3 )-methyl )-dithiophosphate 5 parts of the sodium lignin sulphonate 1 part of the sodium dibutyl naphthyl sulphonate 54 parts of silica b. 50 parts of the active substance of the formula I,

0,0-diethyl-S-(oxazolo[4,5-b]pyridin-2(3H)- onyl(3)-methyldithiophosphatc 5 parts of alkylaryl sulphonate (Tinovetin B") 10 parts of calcium lignine sulphonate 1 part of Champagne chalk-hydroxyethyl cellulose mixture (l:l)

parts of silica 14 parts of kaolin;

c. parts of the active substance of the formula I, e.g. 0,0-diethyl-S-(6-chloro-oxazolo[4,5-b]-pyridin- 2( 3H )-onyl( 3 )-methyl )-thiophosphate 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates 5 parts of naphthalene sulphonic acid/formaldehyde concentrate 82 parts of kaolin. The active substances are intimately mixed with the additives in suitable mixers and ground on mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrate The following constituents are mixed together to manufacture (a) a 10% and (b) a 20% emulsifiable concentrate:

a. ll) parts of active substance of the formula I, e.g. 0,0-dimethyl-S-{6-chloro-oxazolo[4.5-b]-pyridin- 2(3H)-onyl-(3)-methyl]-dithiophosphate l0 parts of a composite emulsifier (fatty alcohol polyglycolether and ethyl arylsulphonate) 40 parts of dimethylcyclohexylphthalate 40 parts of tetralin;

b. 20 parts of active substance of the formula I, e.g.

0,0-diethyl-S-[6-chloro-oxazolo[4,5b]-pyridin- 2(3H)-onyl(3)-methyl]-dithiophosphate 20 parts of dioxane l0 parts of a composite emulsifier (fatty alcohol polyglycolether and alkylaryl sulphonate) 50 parts of tetralin. This concentrate can be diluted with water to form emulsions of any desired concentration.

Spray The following constituents are used to manufacture (a) a 5% and (b) a 2% spray:

a. 5 parts of active substance of the formula I, e.g.

0,0dimethyl-S-[oxazolo[4,5-b]pyridin-2( 3H )-onyl- (3 )-metl1yll-dithiophosphate l part of epichlorohydrin 94 parts of petroleum l 60 1 C b. 2 parts of active substance of the formula I, e.g.

0.0-dimethyl-S-[6-chloro-oxazolo[4,5-b]-pyridin- 2( 3H )-onyl( 3 )-methyl l-dithiophosphate 3 parts of 4,4'-dichlorodiphenyl-trichloroethane 95 parts of kerosene.

These solutions are sprayed with a pressure sprayer.

Anti-helminthic preparations of the new phosphorus compounds of the formula I are described herewith below. The parts denote parts by weight.

ether (boiling limits Active substance concentrate in paste form Such semisolid or oily active substance concentrates have, for example, the following composition:

a. 40 parts of active substance of the formula I, e.g.

0,0-diethyl-S-[6-chloro-oxazolo[4,5-blpyridin 2( 3H )-only-( 3 )-methyll-dithiophosphate 10 parts of bolus alba 2 parts of sodium lignin sulphonate 0.2 parts of sodium benzoate 1.0 part of carboxymethyl cellulose 46.8 parts of water;

b. 30 parts of active substance of the formula I. e.g.

0,0-bis-(2'-chloroethyl)-S-[oxazolo[4,5-bl-pyridin- 2( 3H )-onyl-( 3 )-methyll-dithiophosphate 70 parts of ground-nut oil.

The active substances are very finely ground with the carriers, dispersants and other additives (particle size 5-l0 microns).

Powder concentrate The following substances are used to manufacture (a) a 50% and (b) a 25% powder concentrate:

a. 50 parts of active substance of the formula I. e.g.

11 12 0,0-diethyl-S-ioxazolo[4,5-b]pyridin-2(3H)-onyl- (3)-methyll-dithiophosphate 3 parts of polyoxyethylene-sorbitan-monooleate Cale C 39.5] H 4.53 N 838 P g 28 5 M8 q 3 parts of sodium l1gn1n sulphonate Found C 39.55 H 4,55 N 8,48 P 9 19 S 19,25 it 44 parts of bolus alba', 5

b. 25 parts of active substance of the formula I, e.g.

0,0 diethyl-S-[ ox az0lo{4,5-b]pyridin-2(3H)-thione- Example 3 3-onyl-methyll-dithiophosphate g pans f polyvinyl pyrmlidone Sixty-three grams of the potassium salt of 0,0-bis-( 2- 3 parts f dodecylbenzenesuiphonam 10 methoxyethyl)-dithiophosphoric acid and 37 g of 3- 30 parts of bUlU alba. The indicated active sub- 5mm h T at o e stances are applieo to the carriers, for example in the f h Off In a water J vacuum, the form of acetonic solutions. The dispersants and wetting resldue treated whh 300 ml of water and the that agents are added Subsequently and the concentrate is has separated out is taken up in ether. The ether soluground to homogenehy tion is washed with sodium bicarbonate and water,

dried, and the ether is distilled off. The residual oil is Example 1 freed from volatile fractions by heating to 70C in a one hundred and nine grams oxazolomai 2 high vacuum and subsequently filtered through an anib]pyridine-2-(3H) one J. Frazer and E. Tittenser, .I. 0 mal charcoal filter I Chem. Soc. (London) i957, 4625 are stirred in a mixslxty'three grams, 9 mithoxy'ethyns' ture of 100 g of approx. 37% aqueous formaldehyde soh h f B l'methyll' lution and 600 ml of water for 9% hour at room temperadnhlophoshhzhe are P the f of a pale ture and far 1 hour at 5036000 After cooling. filtra low, non-diztillable oil, which is a Single substance in tion and drying to filtrate, 126 g of 3-hydroxymethylthmdayer C romamgrdm' oxazolo[4,5-b]-pyridine-2(3H)-one are obtained (mp. 155C, with decomp.).

b. One hundred and twenty-six grams of 3- Calc. C 39.59 H 4.86 N 7,10 P 7.87 8 16.26 1 hydroxymethyl-oxazoloi4,5-b]pyridine-2-(3H)-one Found of are suspended in 1200 ml of chloroform. 126 Grams of thionyl chloride are run in rapidly, the mixture is stirred initially for half an hour at room temperature, then for Example 4 3 hours at 60C, cooled andthe undissolved impurities Fortymine grams of O ethy dithi0 are filtered off. The filtrate 1s evaporated to dryness in phfinylphosphonic acid and 37 g of 3 chlommthyl a water et vacuum, the residue m1xed with petroleum oxazolo[45 b]pyfldine 2(3H) One are dissolved in 200 ether and hheredj yeld g of 3'chlorometl1yl' ml of acetone. While stirring, a solution of 9 g of so- Oxazolol45b]Py"dme'2(3Hlohe 10904 H dium hydroxide in 40 ml of water is added dropwise Grams of 3'chlommethyloxazhlol4,5 and the mixture is then heated for 4 hours to 35C. The lPY and 2| 8 of the ammohhhh salt 40 acetone is distilled of in a water jet vacuum, the residue of OD-dimeihyldhhihphosphate are stirred in loo m] treated with 200 ml of water and extracted with ether. of acetone for 4 hours at 100 Mhhhtres of water The ethereal extract is washed until neutral, dried and are added and the acetone is distilled off in a water jet dismled ff to leave a rapidly congealing Recrystalvacuum at 35C. The crystals that have separated out lisation f 300 m] f methanol i td 37 g f 0. are filtered off and recrystallised from methanol, to h s i 4 5 i 2 3 3 g Of O,O-dimethyl-S-[0xazolo[4,5-blpyridinemethyl1*jithkyphenylphogpha; 2(3H)onyl-(3)-rnethylldithiophosphate (m.p. 707 1C).

Cale. C 49,16 H 4J3 N 7,64 P 8,47 S [7,50 71 Found 49.10 4.20 7,6t 8166 17,20%

Cale. N 9.15 P l0,t S 20,9 a Found N 9.3 P 10.0 5 20,9 7

Example 5 a. Two hundred and four grams of oxazolo[4,5- Example 2 b]pyridine-2(3H)-one are dissolved in 1500 ml of dimethylformamide. At 20-25C, lll g of chlorine are one hundred and ygrams of the Pmassium introduced into the solution within 2 hours. The mixl of 0,0-diethyldithiophosphoric aCid ar COVBTEd ture is further stirred for 1 hour and poured into 3 litres with a whim)" of 134 8 of 3'ChlOrOmethYl0XaZ0l0l4.5- of ice water. The product that has crystallised out is fillPY -U lin 300 ml of HCelOflfi- The tered off, washed and dried. Two hundred and twelve ture is stirred for 4 hours at 35C, then the bulk of the grams of fi chloromxazolo [4,5 b]pyridine-2-(3H )-one acetone is distilled off in a water jet vacuum and the (m,p l87-l88C) are obtained, residue treated with 800 ml of water. The oil that has b. One hundred and thirtyfive grams of (a-chloroinitially separated out solidifies in crystalline form. 6 oxazolo[4,5-b]pyridine-2-(3H)-one, 800 ml of water Recrystallisation from 350 ml of methanol yields I88 g of 0.0-diethyl-S-oxazolo-4,5-b pyridine-2(3H)- onyl(3)-methyl dithiophosphate (mp. 86-87C).

and I60 g of an approx. 37% aqueous formaldehyde solution are stirred for k hour at room temperature and then for 2 hours at 5060C. The mixture is cooled.

the precipitate that forms filtered off, the residue washed with ice water and dried at C in a water jet vacuum. 148 Grams of 3-hydroxymethyl-6-chlorooxazolo[4,5-b]pyridine-2(3H)-one (mp. 138C, with decomp.) are obtained.

c. Two hundred grams of thionyl chloride are rapidly run into a suspension of 240 g of 3-hydroxymethyl-6- chloro-oxazolo[4,5-b]pyridine-2(3H)-one in 1200 ml of chloroform. The mixture is stirred for /2 hour at room temperature, then for 1 hour at C. The by this time clear solution is evaporated to dryness in a water jet vacuum, the residue treated with petroleum pyridine-2(3H)-one (m.p. l04l06C) are obtained.

d. Forty-four grams of 3-chloromethyl-6-chloro- Example 7 One hundred and sixty-six grams of the potassium salt of 0,0diethyl-dithiophosphoric acid and 135 g of 3-chloromethyl-6-chloro-oxa2olo[4,5-blpyridine- 2(3H)-one are dissolved in 800 ml of acetone. The temperature of the reaction mixture slowly rises to 33C. Six hundred milliliters of water are then added and the bulk of the acetone is distilled off in a water jet vacuum at 35C. The oil that has initially settled out congeals to crystalline form. Recrystallisation from 500 ml of methanol yields 170 g of 0,0-diethyl-S-[6- chloro-oxazolo[4,5-b]pyridine-2(3H)-onyl-(3)- methyll-dithiophosphate (m.p. 8l82C).

monium salt of 0,0-diethylmonothiophosphoric acid are stirred in 300 ml of acetone for 4 hours at 60C. The acetone is distilled off in a water jet vacuum and the residue treated with 300 ml of water. The crystalline precipitate that has formed is filtered off and recrystallised from methanol. 42 Grams of 0,0-diethyl-S- [6-chlorooxazolo[4,5-b]pyridine-2(3H)-onyl-(3)- Calc. C 35,82 H 3,83 N 7,60 P 8,42 5 17,39 C19,62 /1 Found 35,85 3,80 7,64 3,31 17,34 9,97 7r oxazolo[4,5-b]pyridine-2(3H)-one and 49 g of the am- Example 8 Forty-two grams of 0,0-bis-(2-chloroethyl)-dithiophosphoric acid and 35 g of 3-chloromethyl-6-chl0rooxazolo[4,5-b]pyridine-2(3H)-0ne are dissolved in 150 ml of acetone. A solution of 6.5 g of sodium hydroxide in ml of water is then added dropwise and the mixture is stirred for 4 hours at 40"C.

methylpdithiophosphate area Obtained (mg The acetone is thereafter distilled off in a water jet o 30 vacuum, 300 ml of water are added and the oily crystal line precipitation that forms is taken up ether. The ether solution is washed with sodium bicarbonate solugg f 3321; 2:98 28; g gg tion and with water. Recrystallisation twice from a small amount of methanol yields 22 g of 0,0-bis-(2'- E l 6 35 chloroethyl)-S-[6-chloro-oxazolo-[4,5-b]pyridine- Xamp e 2(3H)-onyl-(3)-methyl]-dithiophosphate (m.p. A solution of 238 g of 3-chloromethyl-6-chloro- 7 l73C.

Calc. C 30,18 H 2,76 N 6,40 F 7,09 S 14,69 Cl 24,30 7r Found 30,23 2,79 6,20 6,96 14,72 24,28 ir oxazolo[4,5-b]pyridine-2(3H)-one in 500 ml of ace- Example 9 tone is slowly added dropwise to a suspension of 255 g orty-five gram of O-methyl-dithioof the potassium salt of 0,0-dimethyldithiophosphoric acid in 500 ml of acetone. The temperature gradually rises to 32C and the mixture is further stirred for 4 hours at 30C. The solvent is thereafter stripped off in a water jet vacuum, the residue treated with ml of water, and the oil that has separated out is taken up in ether. The ether solution is washed with sodium hydrogen bicarbonate solution and with water and the ether is dried and distilled. The residue congeals to crystalphenylphosphonic acid are dissolved in 200 ml of acetone. A solution of 9 g of sodium hydroxide in 400 ml of water is then added dropwise. Thereafter 44 g of Ex. 5 (c) are introduced and the reaction mixture is stirred for 4 hours at 35C. The acetone is then distilled off in a water jet vacuum, the residue treated with 200 ml of water and extracted with ether. The ethereal extract is washed until neutral, dried and the ether distilled off to leave an oil that crystallises gradually.

line form. Recrystallisation from 500 ml of methanol Recrystalllsanon from 500 m] of methanol y l l 23 yields, 198 g of 0,0-dimethyl-S-[6-chloro-oxazolo[4,5- g of y -I q lwpy lb]pyridine-2(3H )-mcthyll-dithiophosphate (m.p, t l-o y t3)- y l- -p y p p -p- 7s-s0c). -107c Cale. C 43,47 H 3,13 7,24 F 8,02 S 16,57 C1 9,17 7r Found 43,41 3,24 6,97 8,03 16,52 9,25 9:

Cale. C 31,72 H 2,96 N 8,23 P 9,11 5 18,82 (I 10,419; Found 31,83 2,95 8,28 8,89 18.53 10,637

Example 10 a. Two hundred and four grams of oxazolo 4,5-b pyridine-2-(3Hl-one are dissolved in 1500 ml of dimethylformamide. Two hundred and sixty-four grams of bromine are slowly added dropwise at room temperature, the mixture is stirred for 1 hour and poured into 9 litres of ice water. The crystalline product that forms is filtered off and dried in vacuo at 50C, yielding 249 g of 6-bromo-oxazolo{4,5-b]pyridine-2( 3H )-one (m.p. 230232C).

b. One hundred and seventy-three grams of 6-bromo oxazolo[4,5-b]-pyridine-2(3H)-one, 900 ml of water and 100 g of an approx 37% aqueous formaldehyde solution are stirred for /2 hour at room temperature and then for 1 hour under reflux. The mixture is cooled, the precipitate that forms is filtered off, washed with ice water and dried at 40C in vacuo, yielding 184 g of 3' hydroxymethyl-6-bromoxazolo[4,S-b]pyridine 2(3H)-one (decomp. at 130C; with splitting off of formaldehyde).

c. One hundred and thirty-three grams of thionyl chloride are run rapidly into a suspension of 183 g of 6-bromo-oxazolo[4,5-b]-pyridine-2(3H)-one in 1500 ml of chloroform. The mixture is stirred for 56 hour at room temperature and then for 2 hours at 60C. The by now clear solution is evaporated to dryness in a water jet vacuum, the residue mixed with petroleum, filtered off and dried, yielding 192 g of 3-chloromethyl-6- bromo-oxazolol4,5-b]pyridine-2(3H)-one (m.p. 129-130C).

(1. One hundred and sixteen Grams of 3-chloromethyl -6-bromo-oxazolo [4,5-b]pyridine-2(3H)-one and l 19 g of the potassium salt of 0,0-diethyldithiophosphoric acid are stirred for 4 hours at 35C in 600, l of acetone. The acetone is then distilled off in vacuo and the residue treated with 600 ml of water. The oil that has separated out congeals to a crystalline form after it has been thoroughly stirred. Recrystallisation from methanol yiels 136 g of O,o-diethyl-S-l6-bromo-oxazolo[4,5- b]pyridine-2( 3H )-nyl-( 3 )methyl]-dithiophosphate (m.p. 98-99C).

Cale. C 3|,97 H 3,42 N 6,78 P 7,5l S 15,52 7r Found 32,09 3,37 6,87 7,36 15,48 7 Calc. Br I933 it Found 19,88 ii EXAMPLE 11 (3H )-onyl-( 3 )-methyll-dithiophosphate (m.p. Eff-87C).

Calc. N 7.27 16,64 P 8,05 /r Found 7,3 16,4 7,9 'l' EXAMPLE 12 (3H )-onyl-( 3 )-methyl]-dithiophosphate (m.p. 65-67C) crystallise on cooling.

Cale. C 35,37 H 4,11 N 6,35 P 7,03 5 14,53 Found 35,35 3, 5 6,31 7,02 14,56 It Cale. Br 18,28 '70 Found 1906 By using 55 g of the potassium salt of 0,0-diallyldithiophosphoric acid and proceeding in a manner analogous to the above Example, 42 g of 0,0 diallyl-S-[ 6-bromo-oxazolo[ 4,5-b]pyridin-2( 3H )-onyl- (3)-methyl]-dithiophosphate are obtained (m.p. 3840C).

Calc. C 35,71 H 3.22 N 6,41 P 7,10 5 14,66 '1 Found 35,35 3,16 6,56 6.85 14,31 it Cale. Br I828 7t Found l9,06 4

EXAMPLE 13 a. One hundred and fifty-two Grams of oxazolo 4,5-b pyridine-2(3H)-thione [T. Takahashi and F. Yoneda, Pharm. Bull. (Tokyo) 5, 350 (1957)] in a mixture of g ofa 37% aqueous formaldehyde solution and 600 ml of water are stirred for 5: hour at room temperature and subsequently for 2 hours at 60C. After cooling, filtration and drying the filtrate, g of 3- hydroxymethyl-oxazolo[4,5-b]pyridin-2( 3H )-thione are obtained (no real melting point; splitting off of formaldehyde at 1 10C).

b. 180 g of 3-hydroxymethyl-oxazolo[4,5-blpyridin- 2(3H)-thione are suspended in 1500 ml of chloroform. 167 Grams of thionyl chloride are run in at room temperature, the mixture is stirred for half an hour at the same temperature then gradually heated to 60C and maintained at this temperature for 2 hours. The by now clear solution is evaporated to dryness, the residue stirred with petroleum ether and filtered, yielding g of crude 3-chloromethyl-oxazolo[4,5- blpyridin2(3H)-thione (mp l20-123C).

c. 95 Grams of the potassium salt of0,0-diethyldithiophosphoric acid and 70 g of 3-chloro-methyl-oxazolo 4,5-b pyridine-2(3H)-thione are suspended in 800 ml of acetone. The suspension is stirred for 4 hours at 35 40C, then the acetone is distilled off in a water jet vacuum and the residue treated with 800 ml of water. The oil that has initially separated out congeals to crystalline form. Recrystallization from 400 ml of methanol yields 87 g of 0,0-diethyl-S-loxazolol4,5-b]pyridin- 3,886,274 17 18 2(3H)-thione-3-yl-methyll-dithiophosphate (m.p 64 and the filter cake washed with cold water. After a C thorough drying in vacuo at 40C, l02 g of pale yellow 3-hydroxymethyl-6-nitro-oxazolo[4,5-b]pyridin- 2(3Hl-one are obtained, which decomposes from 5 140C accompanied by splitting off of formaldehyde. 0. One hundred and six Grams of 3-hydroxymethyl-6- nitro-oxazolo [4,5-b]pyridin-2(3H)-one are suspended in 750 ml of chloroform. 5 Milliliters of dimethylformamide are added and 100 g of thionyl chloride are then run in at room temperature. With gradual heating, the

reaction commences accompanied by vigorous development of gas. After the reaction has subsided, the

Calc. Found EXAMPLE l4 Thirty Grams of O-methyl-dithio-methyl-phosphonic acid are dissolved in 150 ml of acetone and treated dropwise with a olution of 9 g of odi h d id mixture is boiled for 1 hour under reflux and all volatile (solid) in 50 ml of water, 44 Grams of 3- hloro rh lcomponents are then distilled off in a rotary evaporator fi-chloro-oxazolol4,S-b]pyridine-2( 3H) ar i at 50C. The residue forms a viscous oil or a crystalline duced into the mixture, whi h i tirred f 4 hours t crust. It is dissolved in ISO ml of ethyl acetate, the solu- 35C. 200 Millilitres of water are then added and the ion i r ated with 75 ml of petroleum ether and fit acetone is removed from the reaction mixture in a tered over animal charcoal. The clear filtrate is treated water jet vacuum. The oil that separates out initially at 45C with petroleum ether (approx. 150 ml) until solidifes to a viscous mass, which is isolated by decantthe onset of turbidity. On cooling, 83 g of pale yellow ing and recrystallised directly from 400 ml of methanol, 3 chloromethyl-6-nitro-O H l t lpy 3H to yield 46 g of O-methylS-[6-chloro-oxazolo-[4,5- one crystallise (m.p. l07-l09C). b]pyridin-2(3H)-onyl-(3)-methyl]-dithio-methyld. Forty-six Grams of 3-chloromethyl-6-nitrophosphonate (mp 7779C). oxazolo[4,5-b]-pyridin-2(3H)-one and 38 g of the am- Cale. c 33,28 1-1 3,10 N 8,63 P 9,56 5 19,74 CI 10,92 Found 33,50 2,99 8,51 9,54 19,47 11,00

m I i I EXAMPLE I 5 onium salt of 0,0 dimethyl d1th1ophosphor|c 0,0

acid are dissolved in 150 ml of acetone and the solution is stirred for4 hours at C. The solvent is then distilled q4 5 2 3 and g g f of fin a water jet vacuum at 40C, the residue istreated methyl-N,N-dimethyl-dithiophosphoric a id id are with water and the oil that has separated out rs taken dissolved in I ml of acetone. A solution of 5 g of so- 35 P m l After g p ly Shaken out Wllh dium hydroxide (Solid) in 25 ml f wmer is then added drum bicarbonate solution and with water, the ether sodmpwise and he mixmw is Stirred f 4 hours at lution 1s dried and the solvent d1st1lled off. The residual Th b lk f he Solvent is subsequenfly distilled ff in Oil crystallises after a t1me. Recrystallisation twice from a water jet vacuum and the residue treated with 100 ml 9 the amPum of meihanQl P 0 2 g of L of water. The oil that has separated out is crystallised 40 y 'l ?'Q l lPY" -3( :l-

at once. Recrystallisation from methanol yields 25 g of W y lp p -P El O methyl-N,N-dimethyl-S-[6-chloro-oxazolo[4,5-b]- Twenty-two Grams of 3-chloromethyl-6-chl0ropyridin-2( 3H)-onyl-(3 )-methyll-dithiophosphoric ami- Cale. C 30,77 H 2,87 N H.961 P 8,84 s l8,25 92 date p o e Found C 30,80 H 2,84 N l2,04 F 8,84 S l8,27 Zr Calc. C 33,95 H 3,70 N ll,89 P 8,77 S 13,77 Cl 10,02 Found 34,20 3,75 l2,l9 8,66 l8,06 l0,l8

EXAMPLE 16 Example 17 a. Two hundred and seventy-two Grams of oxazolo[- 4,5-b]pyridine-2-(3H)-one are introduced at 5 to 5C into 800 ml of concentrated sulphuric acid. Thereafter 400 ml of fuming nitric acid are added dropwise at 0l0C and the mixture is left to stand for 3 to 4 days at room temperature. The reaction mixture is then poured onto 3 kg of ice, the precipitated nitration prodevaporator. The Oily residue is treated with ice, then uct filitered off and recrystallised from ethanol/water crystallised. Recrystallisation from aqueous methanol to yield 141 g of the pale yellow 6-nitro-oxazolo[4,5- yields 54 g of 3-vinyl-oxazolol4,5-blpyridin-2(3Hl-one b]pyridin-2(3H)-one (m.p.225C accompanied by pre- (m.p. 55-57C). vious conversion at 200C). b. Thirty-two Grams of 3-vir1yl-0xazolo[4,5-

b. Ninety Grams of 6-nitro-oxazolo[4,5-b]pyridinb]pyridin-2(3H)-one and 45 g of diethyl-dithiophos- 2( 3H )-one are suspended in 550 ml of water. One hunphoric acid are disolved in 150 ml of toluene and boiled tired and ten Millilitres of an approx 37 71 aqueous forunder reflux for 8 hours. The reaction mixture is then maldehyde solution are then added and the mixture is cooled, diluted with ether and shaken out with sodium stirred for a hour at room temmperature and then for bicarbonate solution and with water. The ethertoluene 2 hours at 60C. The resulting paste is o l d. filtered solution is dried and the solvent is distilled off. The rea. To 344 g of vinyl acetate are added initially 5.6 g of mercury acetate and then 075 g of sulphuric acid monohydrate, 65-5 Grams of oxazolo[4,5-blpyridine- 2-(3H)-one are then introduced and the mixture is heated for 7 hours under reflux. The mixture is then cooled, filtered until clear and concentrated in a rotary sidual oil crystallises slowly. Recrystallisation from 70 ml of methanol yields 37 g of 0.0-diethyl-S- [oxazolo[4,5-b]pyridin2( 3H)-onyl-(3 )-ethyl-(l )1- dithiophosphate (m.p. 394lC).

Cale. Found Example 18 a. To a solution of 32.4 g of 3-vinyl-oxazolo[4,5- b]pyridin-2(3H)-one in 200 ml of carbon tetrachloride are added slowly dropwise while cooling with ice at -l0C 32 g of bromine dissolved in 100 ml of carbon tetrachloride. The reaction solution is filtered until Cale. C 48.9 H 254 N 14.27 0 16.3 Cl 18,] 2 Found 48.6 2,7 14,1 16.8 18.0 'K' CalC. C 37.65 H 4,22 N 7.31 P 8.10 S 16.75 Cl 9,26

clear and evaporated in a rotary evaporator. The resid- Example 20 ual oil crystallises on cooling. The crystallised product is triturated with 120 ml of petroleum ether and filtered, to yield 57 g of 3 (l',2'-dibromo-ethyl)- oxazol0[4.S-b]pyridin-2(3H)-one(m.p. 70-72C).

Calc. Found Br 49.7 N 8,7 30,0 1,9 8 ,8

a. To a solution of 98 g of 3-vinylt-chlorooxazolo[4,5-b]pyridin-2(3H)-one and 0.2 g of hydroquinone in 800 ml of carbon tetrachloride are slowly added dropwise while cooling with ice at 0-l0C 80 g of bromine dissolved in 200 ml ofcarbon tetrachloride. The reaction mixture is filtered until clear and evaporated in a rotary evaporator. The crystalline residue is triturated with 300 ml of petroleum ether and filtered to yield 161 g of 3-( l ',2'-dibromoethyl)-6-chlorooxazolo[4,5-b]pyridin -2(3H)-one (m.p. 7l-73C).

Cale. C 26,9 H 1.4 BI 449 C1 9,9 N 7.8 t Found C 26.1 H 1.4 Br 44,5 C1 10.1 N 8,5 7r

b. 71 Grams of 3-( l ',2'-dibromoethyl)-6-chlorooxazolo[4,5-b]pyridin-2(3H)-one and 48 g of the potassium salt of 0,0-diethyl-dithiophosphoric acid are dissolved in 250 ml of acetonitrile and the solution is Calc. C 30.08 H 3.03 N 7,02 P 7.76 S 16.06 Br 20, 2 "70 Found 30,19 3,03 7.06 7.84 16,00 20,12 7r Example 19 50 stirred for 4 hours. The bulk of the solvent is then distilled off in a water jet vacuum and the residue is treated with 300 ml of water. The oil that has separated out is taken up in ether, the ether solution is washed with sodium bicarbonate solution and with water, dried. and the ether distilled off. 86 Grams of a pale yellow, non-distillable oil are obtained, which consists largely of 0,0-diethyl-S-[6-chloro-oxazolo[4,5- b]pyridin-2(3H)onyl-(3 ]-(2"bromoethyl l dithiophosphatc Calc. 11.2 H 3.1 Br 17. (17.7 N (1.1 P 6.7 s 13.9 '21 Found C 11.9 H 3.4 Br I63 ('1 7.7 N 6.1 P 6.7 S 14,2 '71 product are obtained (m.p. l02l04C). Recrystallisa- Example 21 tion from methanol yields 88 g of 3-vinyl-6-chlorooxazolo[4.5-b]pyridin-2-(3H)-one (m.pv 104C).

21. Proceeding in a manner analogous to that described in Example 17. 700 g of vinyl acetate. 1 ml of sulphuric acid monohydrate and 214 g of 6-bromooxazolol4.5-b1-pyridine-2(3H)-one are reacted under refluxv The reaction mixture is then filtered hot until clear and the filtrate evaporated to dryness in vacuo. b]pyridi 2( are reamed as in Example The residue is suspended in water and filtered. One Recrystallisation twice from 150 ml of methanol yields hundred and ninety Grams of crude product are ob- 19 g of 0.0-dimethyl-S-[6-nitor-oxazo1o[4,5 tained. Recrystallisation from 1 100 ml of ethanol yields b]pyridin-2(3H)-onyl-(3 )-ethy1-( 1 ')]-dithiophosphate 147 g of 3-vinyl-6-bromo-oxazolo[4.5-b]pyridin (m.p. 107l10C; mixed melting point with starting 2(3H-one (m.p. 110-112c). material 77-80C).

Calc. C 32.87 H 3.31 N 11.50 P 8.50 S 17.56 7: Found C 33.00 H 3.45 N 11.51 P 8.18 S 17.47 Z

Compounds melting point Cale. C 39.85 H 2.011 Br 33.2 N 11.6 '1 Found C 40.2 H 2.1 Br 32.8 N 11.6 71 Qo-dlcthyLS-loxazolol4.5-b|pyr1d|n-2(3H)-ony1- 38 39 (3] mcthy1 I-Ihiophosphatc 0.0-di-isopropyl-S-1oxazo1o|4.5 bIpyridin-Z- 61 63" b. Th1rty-e1ght Grams of 0.0-d1methyl-d1th1ophos- (3H)...,ny| (methylrdnhmphqsphmc phoric acid and 48 g of viny1-6-bromo-oxazo1o14,5- "Y -1w l 1P l y (3j-methy1]-d1lh1ophosphate b]pyr1d1n-2(3H)-one are dlssolved 1n 120 ml of anyovqpisyz'chlomethyl) S loxumlplfmbb 68 drous benzene and boiled under reflux for 8 hours. The PY W- M' y l-q p p d d h h d O-methy1-S-[oxazo1o[4.5-b]pyr1d1n-2(3H)-ony|- 95 97 reaction mlxture 1s coole 1 ute wit et er an uymgthyldimimphenylmhosphonate shaken out with sodium bicarbonate solutlon. The .01 py -l m 91 1- 43 5 I f] d pyr1d1n-2( Hl-onyl-(Ii)-methyll-dlthrophosphatc Produlct 15 cfystdlllsed from the ether Solutlmh 0.0-bis-(2 -rnethoxy-ethyl)-S-lb-chloro-oxazolonon-distillable 011 and recrystallised from 900 ml of methanol to yleld S6 l g lgy g fl3 y y l- 1 top 05p ate g of 'l 0.0-dia1ly1-S-l6-ch10rooxazo1o[4.5-b1pyridin- 2s 29 2( 3H )-0ny1( 3 )-ethyl-( 1 ')]-d1th1ophosphate (m.p. 2(3H)-0nyl(3)-methy1]-dithiophosphate o n O-ethyl-S-l6-chlorooxazo1o[4.5-b]pyr1din-2- 66 68 1 15 l 17 C).

Cale. C 30.08 H 3.03 N 7.01 P 7.77 5 16.06 Br 20.02 11 Found C 30.18 H 3.01 N 7.01 P 7.55 5 16,17 Br 20.21%

(3H)-onyl-(3 )-methy1]-dithiophen 1 hosphonate E p 22 0,0-diethy1-S-[6-bromo-oxazololl blpyridin-2- 5s 60 (3H )-onyl( 3 )-methyl I-thiophosphate a. To 240 g of vmyl acetate are added successively 0,0-bis(2' methoxy-ethyl)-S-16-bromo-oxazolonon-distillable 011 03.6 g of mercury acetate, 0.45 g of sulphuric acid lP l- "W 4 ly l- 4 5 dithlophosphate monohydrate and 54 g of 6mu'ooxazolol O.O-bis-(2 'chloro-ethyl)-S-{6 bromo-oxazo1o- 88 91 b]pyridin-2( 3H)-one. The mixture is stirred for 2 hours 40 l4. 1py dm2(3H)-onyl-(3)-methyl]- I o l I t ated d1th1ophosphate d1 C and the y C Bar so P P F 0.0-dimethy1-S-[oxa;o1o[4.5-b1pyridin-2(3H)- s3 85 in a rotary evaporator. The crystalhne residue is stirred glole-lsylignegltylI-dlthiophfighgfie d 2 56 58 I I -et yc orocxazoo pyn 1nwith cold water. filtered, and the filtrate crystallised (3H) Qnyl (3)qnflhylrdithiwmmhylphosphum from 250 ml of ethanol to yield 41 g of pale yellow 3- *Calc. C 36.40 H 4.23 N 6.53 P 7.23 S 14.95 Cl 8.27 Found 36.9 4.3 6.8 6.8 14.5 9.1 7v *Calc C 32.99 H 3.84 N 5.91 P 6.65 5 13.55 Br 16.88 Found C 33.1 H 3.8 N 5.9 P 6.2 S 13.0 Br 17.5

Compounds melting point 0.0-dirnethyl-S[oxazolo14.5-b1pyridin-2( 3H ony1-(3 l-methyl |-thiophoshate 77 79 0.0-dimethyl-S-[6-brorno-oxazolo[4.51J]pyridin- 2( 3H)-onyi-( 31methy1]-thiophosphate 96 101 0.0-diethyl-S-[6-brorno-oxazo1ol4.5-b]pyridin- 2( 3H )-ony1-( 31-methyll-dithiophosphate 83 O-methy1N.Ndimethyl-S-1oxaz0lo[4.5b|pyridin- 21 3H )-ony1-( 3 )mcthy11dithiophosphorus amidate 44 46 O-ethyLN .N-dimcthy1-S-1 6-ch1oro-oxazo1ol4.5-b| pyridin-2( 3H )-ony1-( 3 )-mcthy1l-clithiophosphorus non-distillamidatc able 0.0-dimethy1-S-1oxazoloi4.5-b1pyridin2( 3H non-disti11 ony|-[3)-ethy1 1') l-dithiophosphatc able oil 0.0-dimcthyl-S-[6-ch1oro-oxazo1o14.5-1)lpyridin- 2(3H )-ony1-( 3)cthy1-( 'll-dithiophosphate 103 105 0.0-dicthyl-S-16-bromo oxazolol 4.5'blpyridin- 2( 3H )-onyl-1 3 1-cthyl-( l'll-dithiophosphate 68 70 0.0-Ll1'.lh \l'S-i[3148101014.5-blpyl'1dl1b2l3H ong1'13)-(Zbromocthy1|-[1')|-dithiophosphutc 30 32 O.O-dicthy1 S-[b-nitro-oxazolol4.5-1'1Ipyridin- 2.1 3H )-ony1-( 3 ]-ethy1-( l) Idithiophosphatc 103 105 *Culc. C 3 .92 H 4.11 N 11.43 P 8.44 S 17.44 Cl 9.64 .1 Found C 36.3 H 4.1 N 11.5 P 7.9 S 16.9 C1 10.0 r C1|lc. C 37.40 H 4.0) N 8.75 P 9.69 S 20.02 ",1 Found C 37.6 H 4.1 N 8.5 P 9.6 S 20.4 C1

Compounds melting point 74 a 76 non distill able oiP 2( 3H)one-3-yl-methy])dithioethylphosphonate 55 56 0.0-dimethyl-S-( oxazolot 4.5-b)pyridin2( 3H one-3-yl-( 2'chloroethyl)-( l '))-dithiophosphate 66 68 O O-dimethy] S(6-chloro-oxazolo(4,5-b)-phyridin- 2( 3H )-onc-3-yl-( 2 '-brom0ethyl)-( 'J)-dithionondistill phosphate able oi] 0,0'dimethylS-l6-bromo-oxazolo(4,5-b) yridin- 2(3H)-one3-yl-(2'-hromoethyl]-( I '])-dit io non-d1st|llphosphate able oil *Culc, I C 39.47 H 4.3] N 9,2] l(l.l8 S ZLOB Z Found 39.5 4,6 8,8 IO.3 20.8 CaIc; C 27.69 H 2.56 N 6,47 P 7.]6 Cl 8.]8 Br l8,43 k

Found: 28,2 2.6 6.5 7.] 7,9 18,8 9] ******Calc.: C 25.12 H 2.32 N 5.86 P 6.49 s |3,4| Br 3 Found: 25,) 2.5 5.6 6.] [2.8 33,3 7r

Example 23 water of crystallisation are refluxed for 10 minutes m Five hundred and forty-eight Grams of 3- chloromethyl-6-chloro-oxazo]0[4,5- blpyridine-Zt 3H)-one, 480 g of the ammonium salt of 0.0-dimethylmonophosphoric acid and I200 ml of methanol are heated to the boil as quickly as possible while stirring thoroughly and refluxed for 5 minutes.

50 ml of methanol. The solvent is distilled off in a rotary evaporator and on treating the residue with 100 ml of water a crystalline filling is obtained. Recrystallisation from 200 ml of aqueous methanol yields ]7 g of O- ethy]-S(6chloro-oxazolo(4,5-b)pyridin-2(3H)-one-3- yl-methy])-thiophosphoric amidate (mp from ]]0C with decomp.).

Cale: C 33.39

H 3.43 N 12,98 P 9.59 S 9.9] CI ]U.95

7? Found: 33,72 3.55 12,9] 9,37 9.89 ]].O7 9? Example 26 at Proceeding in a manner analogous to that described in Examples ]8a and 20a. 3-(l'.2- dibromoethy])-6-bromooxazolo(4.5-b)pyridin- 2(3H)-one is manufactured from 3-vinyl-6-bromooxazolo]4.5-b]pyridin-2(3H)-one (m.p. 84-86C).

Calc: C 33,29 H 3,]! Found: 33,56 3.]3 8.52 9,62 9.78 l

Example 24 Thirty-two Grams of 3-( l ',2'-dibromoethyl)- oxazolo(4,5-b)pyridine-2(3H)-one are introduced into a solution of 19 g of the ammonium salt of 0,0-dimethyl-dithiophosphoric acid in ml of water. 50 The mixture is stirred for k hour at -70C so vigorously that the fused dibromo compound is well emulsifled. The oil layer congeals to a crystalline state on cooling and afterr recrystallisation yields 26 g of 0,0-dimethyl-S-(oxazolo (4.5 b)-pyridin-2-(3H)-one- 55 3-yl-( 2'-bromoethyl)-( l'))dithiophosphate (m.p. KP-C), which is identical with the compound of Example ]8 b.

Example 25 60 Twenty-two Grams of 3 -chloromethyl-6-chlorooxazo]o[4.S-b]pyridine-2(3H)-one and 20 g of the sodium salt of Oethyl-thiophosphoric acid containing Cale: C 23.95 H l. Found: 24,l l.

b. Forty Grams of 3-( l,2'-dibromoethyl)-6-bromooxazolo(4.5-b)pyridin-2(3H)-one and 24 g of the potassium salt of 0.0-diethyl-dithiophosphoric acid are suspended in 50 ml of methanol and refluxed for 10 minutes. The solvent is then distilled off in a rotary evaporator and the residue is treated with ml of water. The viscous oil that has separated out is taken up in ether, the ether solution washed with sodium bicarbonate solution and water. dried. and the ether dis tilled off. Fifty-one Grams of 0,0-diethyl-S-(6-bromooxazolo( 4,5-b )pyridin-2( 3H )-one-3-y]-( 2 bromoethyl)-( l ))-dithiophosphate are obtained in the form of a pale yellow. viscous, non-distillahle oi].

Cale: C 28.47

Found: 29.]

Example 27 a. Chlorine gas is introduced while cooling with ice at 0l0"C into a solution of 243 g of 3-vinyloxazolo[4,5-b]pyridin-2(3H)-one and 0.6 g of hydroquinone in 1500 ml of carbon tetrachloride. The reacmixture is then heated briefly to 60C, the bulk of the methanol is evaporated off in a rotary evaporator, the residue is treated with water and extracted with ether. Recrystallisation from 30 ml of methanol yields 13 g 0,0-diethyl-S-(oxazolo(4,5-b)pyridin-2(3H)-one-3-yl- (2-chloroethyl)-l l )-dithiophosphate (m.p.

tion solution is then filtered clear and concentrated in 47.48C)

Calc.: C 37,64 H 4,21 N 7,32 P 8 11 S l6 75 (19,26 Found: 37,48 4,37 7.34 8,07 l6,7l 9,50

a rotary evaporator. The initially oily residue is stirred with petroleum ether until it has thoroughly crystallised. The crystalline product is then filtered off and 220 g of 3-( l ,2-dichloroethyl )-oxazolo[4,5- b]pyridin-2-(3H)-one are obtained (m.p. 5862C).

Cale: C 41,2 H 2,58 Cl 30,47 Found: 40,9 2,6 30,4

By proceeding analogously, the two corresponding If the same reaction takes place in acetonitrile instead of in aqueous methanol over 4 hours at 60C, the same product is obtained in poorer yield and purity (mp. 47C).

Example 28 Calc.: C 37.44 H 4,00 Cl l0,65 N 794 S 10,!8 P 8,77 Found: 37,28 4,l5 l0,22 8,04 17,96 8,66 7:

3-(l',2'-dichloroeth l) derivatives are obtained from Exam le 29 3-vinyl-6-chloro-oxazolo[4,5-b]pyridin-2(3 H)-one and 3-vinyl-6-bromooxazolo[4,5-b]pyridin-2(3H)-one; m.p. -64C and 73-75 respectively.

Br 25,6 Cl

"COG

Determination of the anthelminthic action in hens infected with Ascaridia galli One to 3 days old chicks are artificially infected with eggs of Ascaridia galli (roundworms). Groups of chicks each were used per test. Four to 5 weeks after the chicks had been infected, the active substances were administered in one dose per day on three successive days. Infected chicks that were not treated were used for control purposes.

Evaluation The number of Ascaridia gallia rejected per test group over the course of 5 days after the first adminitration of active substance was determined daily and the number still found in the intestine of the 5th. day was likewise determined on dissection. Furthermore, the number of chicks free from worms was determined.

Active substance Daily dosage Number of ascaridia of 5 chicks Number of in mg per g worm-free body weight rejected during period found chicks of test on dissection absolute in of to number tal number 0,0-di-isopropyl-S-[ oxazolol 4.5 -b

pyridin-Zi 3H l-onyl-l 3l-mcthyl I-di- 750 68 100 0 5 thiophosphatc dithiophosphalc QO-dielhyl-S-l b-chloro-oxuzolo-l 4.5-b I pyridin-2( 3H )-onyl-( 3 l-mcthyl l-dithit 750 75 I00 0 5 phosphate pyridin-Jl 3H l-unyl-t 3 )-methyl l-dithio- 750 82 0 5 phosphate Example 30 Tests on mice infected with Syphacia obvel. and Nematospiroides dubius Five mice each infected simultaneously with oxyurae (Syphacia obvel.) and trichostongylidae (Nematospiroides dubuis) were freely fed with feed meal containing 0.2% of active substance. The mice were dissected on the 6th. day of the test and the number of worms present in the intestine was counted. Untreated mice that were simultaneously infected in the same way were used for control purposes.

Example 3] a. Insecticidal Contact poison action a.. For the test on polyvalent resistant house flies, mosquitoes (Aedes aegypti) and stable flies (Stomoxys calcitrans), coatings of active substance from acetonic active solutions in Petri dishes are applied in the following concentrations:

a. 10 mg active substance/dish (for Musca) b. l mg active substance/dish (for Aedes) c. l g active substance/m (for Stomoxys) After 1 hour the dishes are filled with the test subjects. The following table indicates the time after which all subjects are on their backs.

Active substance Daily dosage Total dosage Infection of test Infection of the con in mg/kg in rng/kg animals on dis trol animals on dis sectlon section 0,0-diethyI-Sloxazolol4 5-b|- pyridin-Zl 3H I-unyl-(3 methyll- 208 l248 Syphacia obvel. Syphacia obvel. dithiophosphate (LO-(HJ-O Nematospir. dub. Nematospir. dub. (LO-O-U-(J 6-8-8- l0 O Odiethyl-S-|oxazol0[4,5-blpyridin-2( 3H l-thione- 3-ylmethyl l-dithiophosphate 175 i050 Syphacia obvel. Syphacia obvel.

(LO-04H) l Nematospir. dub Nematospir. dub. 00O-O-(l 6-8-8- l0 Active substance Flies Mosquitoes Stable flies methylythiophosphate bl)-pyridin-2(3H)-nne-3-yl- 5" 90 30' methyl j-thiophosphate 0,0-dimethyl-S( 6chloro- 3-yl-methyl clithiophnsphate a 20 mg ofa 1% dusting agent are uniformly distributed in Petri dishes. The dishes are then filled with cockroaches (Phyllodromia germanica and Periplaneta americana) and kept under normal conditions at 2224C.

The following table indicates the time after which all animals are in the dorsal position.

Insecticidal contact poison action against cockroaches:

a Grain weevils are sprayed with 2 ml of l% acetonic active substance solution from a distance of 10 cm by means ofa spray jet. Immediately after the application the weevils are transferred to clean Petri dishes and kept at 22C. The following table indicates the time after which all the weevils are in the dorsal position.

Insecticidal contact poison action against grain weevils b. Insecticidal period of activity a. on glass: Petri dishes with active substance coatings of l g of active substance per m are left to stand for 8 days at 24C. Then polyvalent resistant hous flies. mosquitoes and stable flies are placed on the coatings.

b. on wood: the active substances are applied to small planks of wood in a concentration of l g of active substance per m from aqueous suspension. After 8 days the above mentioned test subjects are placed on the planks. The following table indicates the time in hours after which the test subjects are in the dorsal position.

thiophosphute thiophosphute O-cthyl-St tS-chloro-(oxazo- 5" 2" phosphonute c. Systematic insecticidal action y -(P t l -py q I To determine the systematic action, 50 ml of an gig gggfj 60 aqueous emulsion containing 100 ppm of active sub- 0.0diethyLS-(oxazolol4 5-b)J-pyridin: stance (obtained from a 10% emulsifiable concentrate) fi igg zif' bmmoemyn' 50 is poured onto the earth of bean plants in pots per 600 5 0,0-diethyl-S-(oxazolo(4,5-b))pyridin-Z C m a (3 H )-one-3-yl-methyl )4hiophosphate 90' After 3 days, aphids (aph1s fabaelare placedon the pyridirrn3H) one 3 y[ mu1y1)dhhiophosphac p portions of the plants above the 50K]. The aphids are -Q- y l I protected by a special device from the contact and gas ig g' flfg ggx%fgfif 60 action. The test is carried out at 24C and 70% relative pyridir 12(3H)-one-3-ylmethyl) thiophosphate 50' atmespheric humidity 35%???Elli iiifilftllfifi flflfiti ilil' 60' The following table indicates the time in days after phae phate 0,0-din 1ethyl'S-(oxazoloM-b) l-pyridin-Z d insecticidal ingested poison action (3H)imlonc'hbmemyl*dnhwphosphme 5 Potato plants are dipped in a 0.1% aqueous active substance emulsion (obtained from emulsifiable concentrate). After the coating has dried, larvae of the Example 32 Colorado potatoe beetle (Leptinotarsa decemlineata) A i id l action are applied to the plants.

The following table indicates the times in minutes PP m'tes (Tetranychus umcae) TO test and hours after which a" beetles (00% are in the don 40 the acaricldal action, bean leaves that are attacked by Salt position adults, encystments and eggs of the red spider mite (Tetranychus urticae) are treated with an aqueous v emulsion containing the test substance in a concentra- 0.0dimethyl S(oxa.zolo(4,54:))pyridin-one- 30' tion of 0.1 The test subjects are strains of the red B-yLme yU u P P spider mite that are resistant to commercially available phosphorus esters.

Active substances Mortality in it within 6 days at an active substance concentration of 0.l

Adults Encystments Eggs lOU I00 llltl I00 Ill) -Continued Active substances Mortality in within 6- days at an active substance concentra tion of 0.1 92 Adults Encystments Eggs methyl )-thiophosphate (4 5-b)]pyridin2(3HHme-3-yl- 100 I lOO methyl l-lhiophosphate dithiomethylphosphatc ridin-2(3H)-one-3-y|-methyl- 100 100 [00 dithiomethylphosphonate (4,5-b) )pyridin-2(3H)-one-3-y|- I00 300 I00 methyl )-dithio-ethylphosphonate (4,5-b)lpyridin-2(3H)-one-3-yl- I00 I00 I00 methyl )dithio-ethylphosphonate ACti fl aga licks (bOOPhiIUS mi r pl l ity. On the th., lOth. and th. day, oviposition is de- Ten Adults, egg laying ticks of various tra ns ar termined. The eggs are kept for a further days under dipped for 3 minutes in an aqueous emulsion of active the same conditions and the possible hatching rate desubstance in a concentration of O.l The ticks are terminal,

then kept at 27C and relative atmospheric humid- Active substance Tick strain oviposition Hatching rate 0,0-diethyl-S-( oxazolo(4,5

b) )-pyridin-2( 3H )-one-3-yl- Ridgeland 0 methyl l-dithiophosphate 0,0-dimethyl-S'( oxazolo 4.5-b) )-pyridin-2( 3H Biarra normal 0 one-3-yl-methyl )-dithiophosphate thiophosphate (4,5-b))-pyridin-2(3H Biarra 0 0ne-3- l-(Z-bromo-ethybl ithiophosphate 0,0-dimethy1-S-( oxazolo (4,5-b )-pyridin-2( 3H Biarra 0 one-3-yl-methyl l-thiophosphate 0.0-bis-( 2 '-methoxa-ethyl S-( oxaz0lo( 4 5-1: )pyridin- Ridgeland 0 2( 3H )-one-3-yl-rnethyl )-dithiosphosphate QO-diallyl-Sqoxazolo (4,5-b))-pyridin-2(3H)- Ridgeland 0 one-31l-methyl)-dithiophosphate (uxazolo( 4 5-b )pyridin-2 Ridgeland (J (3 H )-onc 3-yl-methyl )-dithiophosphutc thiophosphatc diihiophosphatc dith inphosphatc Continued Active substance Tick strain oviposition Hatching rate O O-dimethyl-SHrchlorophosphate 0.0-dimcthyl-S-(o-chloro- (oxazolo( 4,5-h l )pyridinl Ridgeland O (3Hl-one-3-yl-methyll-thiophosphate ))Pyridin-2[3H]-one Biarra 0 3-yl-methyll-dithio-mcthyl phosphonate 0.0-dimethyl-S-(o-brumooxzr thiophos hate (oxazoloMj-b))pyridin- Ridgeland O 2l3H)-one-3-yl-methyl) dithiophosphate dithiophos hate phosphate 0,0-diethyl-S-((a-bromo- (oxazolo-(4,5 b))-pyridin Ridgeland O 2( 3H )-one-3-yl-methyl Hhiophosphate Biarra l I 0 0,0-dimethyl-S-(oxazolo (4,5-b] )pyridin-2( 3H )-thione Ridgeland (1 3-ylmethyl )dithiophosphate 0.0-diethyl-S-(oxazolo (4,5-b))pyridin-2(3H)-thio Ridgeland normal 0 B-yl-methylrdithiophosphate What we claim is: O I. An insecticidal and acaricidal composition com- Cl prising (l) an insecticidally and acaricidally effective 0 amount of a compound of the formula N N C CH -S-P 2 u O OCH 3 N N 3 3. The compositton of claim 1 in which the compound is R CHSP O ll OR cl Y C O N N 0cm l wherein CH -SP R is hydrogen, chlorine, bromine or nitro. ll OCH R is hydrogen, methyl, chloromethyl or bromo- 0 methyl,

R is alkyl of from I to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkenyloxy of from 2 to 4 carbon atoms. alkoxy-alkoxy having a total of from 2 to 4 carbon atoms halogenalkoxy of from I to 4 carbon atoms, or phenyl, R is alkyl of from 1 to 4 carbon atoms, alkenyl of from 2 to 4 carbon atoms, alkoxyalkyl having a l total of from 2 to 4 carbon atoms, or halogenalkyl of from 1 to 4 carbon atoms. and each of X and Y represents oxygen or sulphur. an

(2) a carrier. R P 2. The composition of claim I in which the com- II 0R pound is Y 4. A method for controlling insects and acarids which comprises applying thereto an insecticidally and acaricidally effective amount ofa compound of the formula wherein R is hydrogen, chlorine, bromine or nitro,

R is hydrogen, methyl, chloromethyl or bromomethyl,

R is alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkenyloxy of from 2 to 4 carbon atoms, alkoxyalkoxy having a total of from 2 to 4 carbon atoms, halogenalkoxy of from 1 to 4 carbon atoms, or phenyl,

R is alkyl of from 1 to 4 carbon atoms, alkenyl of from 2 to 4 carbon atoms, alkoxyalkyl having a total of from 2 to 4 carbon atoms, or halogenalkyl of from 1 to 4 carbon atoms, and

each of X and Y represents oxygen or sulphur.

5. The method of claim 4 in which the compound is o \i N N/ oc a l ca -SP 2 oc n 6. The method of claim 4 in which the compound is CHz-S- OCH OCT-l t I\=o \N N OCH ll OCH 8. The method of claim 4 in which the compound is I /-C O f 0on CH2-SP u CH 9. The method of claim 4 in which the compound is l -c o NN l oca ca -sll cs s 11. The method of claim 4 in which the compound N N l C 12. The method of claim 4 in which the compound N s OCH l u 3 CH S-P 13. The method of claim 4 in which the compound 

1. AN INSECTICIDAL AND ACARICIDAL COMPOSITION COMPRISING (1) AN INSECTICIDALLY AND ACARICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The composition of claim 1 in which the compound is
 3. The composition of claim 1 in which the compound is
 4. A method for controlling insects and acarids which comprises applying thereto an insecticidally and acaricidally effective amount of a compound of the formula
 5. The method of claim 4 in which the compound is
 6. The method of claim 4 in which the compound is
 7. The method of claim 4 in which the compound is
 8. The method of claim 4 in which the compound is
 9. The method of claim 4 in which the compound is
 10. The method of claim 4 in which the compound is
 11. The method of claim 4 in which the compound is
 12. The method of claim 4 in which the compound is
 13. The method of claim 4 in which the compound is
 14. The method of claim 4 in which the compound is
 15. A method for controlling parasitic helminths which comprises applying thereto an anthelmintically effective amount of a compound of the formula
 16. The method of claim 15 in which the compound is 